Hydrogenated reaction product of a rosin ester and maleic anhydride and method for its production



. Patented July 25, 1939 PATENT our-"la r.

amaze HYDROGENATED REACTION PRODUCT F I ANHYD ROSIN ESTER AND MALEIC am)rm'rnon-roa rrs PRODUCTION Irvin w. Humphrey, Wilmington, DeL', minor toHercules Powder Company, W DeL, a corporation of Delaware 1 Originalapplication May 14. 1935,

Divided and t No Drawing.

Serial No. 21.331.

ilmington,

his application February 18, 1938, Serial No. 191,203

19 Claims. (cl. 260-100) This invention relates to a new resinousmaterial and method of producing. V In accordance with the methodembodying this invention maleic anhydride is reacted with a reactiverosin compound containing unsaturated bonds typical of rosin acids andthe reaction product hydrogenated. The resinous material in accordancewith this invention will comprise a maleic anhydride-rosin compoundreaction product, the unsaturation of which is. reduced by hydrogen andwhich contains a rosin acid radical and a reactive anhydride groupderived from the maleic anhydride.

In carrying out the method in accordance, with this invention for theproduction of products in accordance therewith, maleic acidmay be usedin place of maleic anhydride, since it will be converted into maleicanhydride at the reaction temperature. The reactive rosin compound willcomprise rosin, refined or unrefined, rosin esters, rosin oil, abietylalcohol, and the like compounds containing unsaturated bonds typicaloirosin acids, such as abietic acid, pimaric'acid, and

the like.

, By virtue of possessing a reactive anhydride group, thevarious-resinous products in accord-v ance with this invention may bereacted with an alkali, as sodium hydroxide, calciumhydroxv ide,potassium carbonate, -etc., or with a reactive an oxide as calciumoxide, ethylene oxide, etc., or

'with' a'suitable alcohol such as methyl, ethyl, butyl, amyl, propyl,hydroabietyl alcohols, cyclohexanol, benzyl, oleyl, tetrahydrofurfuryl,stearyl, lauryl alcohols, a glycol, as ethylene, butylene,

propylene, or diethylene glycol, glycerol, borneol,

ienchyl alcohol, pentaerythritol, ethyleneglycolmon'oethyl ether,sorbitol, or mixtures thereof,

etc.

The products in accordance with this inven- 46 tion will be adaptablefor use in protective coat- ,ings such as lacquers, varnishes, etc., butfor such use are preferably first converted into one oi their morecomplex esters, by treatment with a polyhydric alcohol, such asethyleneglycol or An excess of thefpolyhydric alcohol maybe used overthat required to combine with the anhydride group and any free hydroxylgroups thus introduced may be esterifled by treatment with an organicacid, such as acetic.

50 citric, succinic, phthalic, abietic, dihydroor tetrahydroabietic,oleic, lin'oleic, butyric, propionic,'lino1enic, stearic, sebacic,pimaric, adipic, iuroic, terpinene-maleic anhydride, pinenemaleicanhydride, butadiene-maleic anhydride,

I {I etc., or mixtures of suitable organic acids, yieldbomyl abietate,tetrahydrofuriuryl ing a product which is also adapted for use inprotective coatings and in plastics. Drying or semi-drying oils may beused to modify the product, if desired.

The method in accordance with this invention for production of the newresinous materials embodying this invention andthe character of thematerial will appear in greater detail .irom the following descriptionand examples.

I For the production of the composition embodying this invention, maleic.anhydride may be reacted with rosin or' a rosin acid, as, for example,abletic acid, pimaric acid, or the, like,

with a rosin acid ester, as an ester of a monohexanol abietate,ethyleneglycolmonobutyl abietate, phenyl abietate, etc., with aninorganic abietate, as, for example, sodium, calcium, aluminumabietates, etc., with rosin oil, abietyl alcohol, or other reactiverosin compound containing unsaturated bonds typical of rosin acids.

The time required for effecting the reaction between maleic anhydrideand a rosin compound of the type indicated will vary with thetemperature used and the reactivity of the particular rosin compoundinvolved. Generally speaking, with a temperature of about C. to about250 C., or higher, the reaction will require from about one to aboutfifteen hours. Where the rosincompoundcomprises abietic acid or one ofits derivatives, the reaction will beefiected at a temperature of about125 C. to about C. in

product, the reaction product will be subjected to treatment bycontacting. in a melted state, or in solution in a suitable solvent, as,for example, ethyl acetate, butyl acetate, toluene, etc., with hydrogenin the presence of a hydrogenation catalyst under various conditions ofpressure and temperature, depending upon the particular reactionproduct't'reated, the solvent used and the type and activity of thehydrogenation catalyst used. Generally speaking, where a base metalcatalyst, as nickel, nickel-copper cobalt, or mixtures thereof, is usedthe treatment will be at a u are-7,420

temperature of about 125 C. to ut 225 C., under a hydrogen pressure oiabout 200 lbs. to

about 15,000 lbs., or within the narrower e about 1500 lbs. to about5,000 lbs. and for a a period of about y to about 2 hours. when a noblemetal catalyst, as platinum, -=dium, or the like, is used, a temperatureof about C.

' to about 50 C. and a hydrogen pressure down to atmospheric will befound eii'ective.

1c Thus, broadly speaking, procedure in accordance with thisinvention'will comprise the formation of a product of the reaction ofmaleic anhydride and a reactive rosin compound having unsaturated bondstypical oi rosin acids, as abletic, 1g pimaric and the like, andhydrogenating the product by treatment thereof with hydrogen undersuitable conditions as indicated.

As illustrative of the preparation oi a resinous material embodying thisinvention in accordw ance with-the method embodying-this invention,

for example, 82 grams of technical ethyl abietate are heated with gramsof maleic anhydride at a temperature of 170 C. for eight hours. Thereaction product 'may then be partially distilled as at a temperature ofabout 225 C.-250 C. under about 5-10 mm. mercury pressure to remove anyunreacted ethyl abietate and maleic anhydride. The'product will amountto about 85 grams of resinous material slightly softer than rosin,having an acid number of about 130 and a saponification number of about250. The resinous product will be fairly pale in color and can be partlyv product will then be separated from the catalyst,

by filtration, and recovered from solution, it

treated in solution, by evaporation on of the solvent.

As a further illustration, for example, 80 parts so of glycerolabiet'ate, A. N. 5.8, thiocyanate value 72.8, are heated with 25 partsof maleic anhydride at 170 C. for 6 hours. Distilling 05 thenon-reactedmaleic anhydride' will leave a i resinous product, A. N. 134, SN. about220, thiocyanate value 1.6. The product is then dissolved in, forexample, ethyl acetate to a concentration of about 15%, and, inadmixture with a powdered nickel catalyst, agitated with hydrogen at atemperature of about 210 C.-220 C. and under a 00 hydrogen pressure oiabout 4,000-4,500 lbs.

As further illustrative, 224 parts of rosin oil are reacted with 56parts of maleic anhydride by heating at about 170 C.,for six hours. Thereaction product is then treated at a temperature '05 of about 225 C.and under a pressure 01' about 5 mm. of mercury to distill ofl unreactedrosin oil. The distillate may amount to as much as onehalf of theoriginal rosin 011, depending upon the acidity, method of production;etc., of the rosin oil. The product in solution is then hydrogenated bytreatment with hydrogen in the presence of, for example, a platinumcatalyst, at a temperature of about 30 C. and under 15 lbs.

hydrogen pressure, and finally separated from W the catalyst andsolvent, if in solution.

As a Iurther illustration, for example, parts of abietic acid or rosinand 54 parts of maleic anhydride are ed and heated at a temperature ofsay C. for say about 3 hours. The

heating is desirably carried out in a bath. on 5 completion of theheating for about 3 hours, the temperature of the bath may be desirablyraised to about 250 C; and the pressure on the reaction reduced, say toa pressure of about 5 mm. mercury, in order to remove small amounts of10 free maleic anhydride. 1

The reaction product will be hydrogenated, for example, by contactinghydrogen with a solution thereof in toluene, at a temperature of about-200 C. and under a hydrogen pressure of 15 about 2000-2200 -lbs.,' inthe presenceot a powdered nickel catalyst, which should be mixed withthe solution. on completion of the hydrogenation the catalyst will befiltered out and the hydrogenated product recovered by distilling oi!the m solvent. a

Various other rosin compounds, as, abietyl al cohol, abietic anhydride,etc., may be reacted with maleic anhydride and the hydrogenation thereofwill be eflected as described above with the use g; of rosin oil, rosinesters and rosin.

Generally about one mo! of maleic anhydride will be used per mol 01 anabietic acid ester, if the latter is derived from a monohydric alcohol,

but the molar proportion 01 the anhydride may 30 range about 0.8 to 1.2,depending chiefly upon the reactivity oi the isomers present in theabietic. acid ester. In event the ester is a diabietate it will normallyrequire twice as much maleic anhydride, while a triabietate will usuallytake three "5 times as much anhydride per mol as a monoabietate.

In proceeding for the preparation of the product, the .maleic anhydrideand the rosin compound may be reacted in solution in a suitable 4osolvent, as, for example, xylene, tetralin, chlorbenzene, etc. Where thereaction is eflected in the presence of a solvent the above proceduremay be followed and the product, after the reaction has been efiected,separated from the solvent by 45 distillation.

Compositions in accordance with this inven-- tion, as-has beenindicated, may be formed by reacting various reactiveroan compoundshaving unsaturated reactive bonds typical of rosin w acids with maleicanhydride following the'procedure exemplified.

The hydrogenated product may, if desired, be neutralized with analcohol, as, for example, a.

monohydric alcohol or a polyhydricalcohol and, I!

if desired, thoughnot necessarily, the alcohol treated product may besubjected to treatment .cation catalyst, as, tor example,toluene-sulphonic acid, sulphuric acid, etc., may be used.

Home decolorizing usually occurs during the 65 hydrogenation process.

Where the treatment is with certain monohydric alcohols, such-as butyl,benzyl, or amyl alcohol, the treatment will involve heating the alcoholtogether with the reaction product under 7 atmospheric pressure at asuitable temperature, say within the range 120 C. to 225 C. 0n the otherhand, where the treatment is with a lower aliphatic alcohol, such-asmethyl, ethyl alcohol.

7 or the like, the treatment generally will involve 75 where thetreatment is with a polyhydric alcohol,

as ethylene glycol, glycerol, sorbitol, pentaerythrite, etc., thetreating will be at a temperature 01' about 200 C.-275 C.

Many of the hydrogenated rosin compoundmaleic anhydride reactionproducts may be partially distilled under vacuum, say about mm.pressure, making a preliminary cut to separate any unreacted reagents,and then distilled up to a bath temperature of about 300 0., making cutsif desired at about 260 C. and 300 C. and leaving a residue. Either thedistillates or the residue may be hydrogenated and then, if desired,treated with alcohols. v

In carrying out the method embodying this invention for the productionof the new resinous composition, it will be understood that the detailsof procedure given above are for purposes of illustration only and thatI do not contemplate limitation of my invention thereto, since variousmodifications in details of procedure may be made without departing frommy invention. It will also be understood that maleic acid may be reactedwith a reactive rosin compound instead 01' maleic anhydride.

This application constitutes a division of my application Serial No.21,381, filed by me. on May 14; 1935, for Composition of matter andmethod 01' producing.

What I claim and desire to protect by Letters Patent is:

' 1. A reaction productof monohydric alcohol ester of a rosin acid andmaleic anhydride, the unsaturation of' the product being reducedbyhydrogen.

2. A reaction product of a monohydric alcohol ester .of abietic acid andmaleic anhydride, the

' unsaturation o! the product being reduced by hydrogen.

3. A reaction product of a monohydric alcohol ester of pimaric acid andmaleic anhydride, the unsaturation oi the product being reduced byhydrogen.

4. A reaction product 01 the methyl ester of abietic acid and maleicanhydride, the unsaturation of the product being reduced by hydrogen.

5. A reaction product of the ethyl ester of abietic acid and maleicanhydride, the unsaturation of the product being reduced by hydrogen.

6. The method of producing a synthetic resin which includes reacting amonohydric alcohol 60 ester of a rosin acid with maleic anhydride andhydrogenating the product in the presence of an active hydrogenationcatalyst.

8. The method of producing a synthetic resin which includes heating amonohydric alcohol ester or a rosin acid with maleic anhydride andhydrogenating the product in the presence of an active, base metal,hydrogenation catalyst.

9. The method of producing a synthetic resin which includes heating amonohydric alcohol ester of a rosin acid with maleic anhydride andhydrogenating the product under a hydrogen pressure from about 1500 toabout 5000 pounds per square inch in'the presence of an active, basemetal, hydrogenation catalyst.

10. The method of producing a synthetic resin which includes reacting amonohydric alcohol ester of abietic acid with maleic anhydride andhydrogenating the product.

11. The method of producing a synthetic resin which includes reacting amonohydric alcohol ester of a rosin acid with maleic anhydride,hydrogenating the product, and neutralizing the hydrogenated product.

12. The method of producing a synthetic resin which includes reactingmethyl abietate with maleic anhydride and hydrogenating the product.

13. The method of producing a synthetic resin which includes reactingethyl abietate with maleic anhydride and hydrogenating the product.

14. A reaction product of a monohydric alcohol and a rosin acid withmaleic anhydride, the unsaturation of the product being reduced byhydrogen, and the hydrogenated product being neutralized.

15. A reaction product of methyl abietate with maleic anhydride, theunsaturation of the product being reduced by hydrogen, and thehydrogenated product being neutralized;

16. A reaction product of a monohydric alcohol ester of a rosin acid andmaleic anhydride, the unsaturation of the product being reduced byhydrogen and the hydrogenated product being neutralized by reaction withan alcohol.

17. A reaction product of a monohydric alcoholester of a rosin acid andmaleic anhydride, the unsaturation of the product being reduced byhydrogen and the hydrogenated product being neutralized by reaction witha polyhydric alcohol.

18. A reaction product of a monohydric alco- I hol ester of a rosin acidand maleic anhydride, the unsaturation of the product being reduced byhydrogen and the hydrogenated product being neutralized by reaction withethylene glycol.

19. The method of producing a synthetic resin which includes reacting amonohydric alcohol ester of a rosinacid with maleic anhydride,hydrogenating the product and neutralizing the hydrogenated product byreaction with an alcoho].

IRVIN W. HUMPHREY.

